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WO2025190675A1 - Composition époxy pour la production d'un composite époxy - Google Patents

Composition époxy pour la production d'un composite époxy

Info

Publication number
WO2025190675A1
WO2025190675A1 PCT/EP2025/055294 EP2025055294W WO2025190675A1 WO 2025190675 A1 WO2025190675 A1 WO 2025190675A1 EP 2025055294 W EP2025055294 W EP 2025055294W WO 2025190675 A1 WO2025190675 A1 WO 2025190675A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy
epoxy composition
amine hardener
structural formula
composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/055294
Other languages
English (en)
Inventor
Pietro BUONO
Helga De Velder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huntsman Petrochemical LLC
Original Assignee
Huntsman Petrochemical LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huntsman Petrochemical LLC filed Critical Huntsman Petrochemical LLC
Publication of WO2025190675A1 publication Critical patent/WO2025190675A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C08G59/5013—Amines aliphatic containing more than seven carbon atoms, e.g. fatty amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen

Definitions

  • the present disclosure relates to an epoxy composition for producing an epoxy composite.
  • the present disclosure also relates to an epoxy composite, a method of producing an epoxy composite, an epoxy composite obtainable by the method described herein, and the use of an amine hardener component in the production of an epoxy composite.
  • the epoxy composition described herein is a simplified epoxy composition for producing an epoxy composite, because only one type of amine hardener may be used as opposed to the usual blend of amine hardeners often required in epoxy compositions for producing epoxy composites.
  • the epoxy composition described herein is particularly useful in the production of epoxy composites which require excellent mechanical strength but where the epoxy composition need sufficient time to flow and impregnate the reinforcement before fully curing, such as in the production of blades for wind turbines.
  • Epoxy compositions therefore comprise a hardener.
  • An epoxy composition may be used to produce an epoxy composite, which is made up of the cured epoxy resin and typically a reinforcement distributed in the cured epoxy resin.
  • epoxy compositions used to form epoxy composites may comprise a blend of hardeners, i.e., the epoxy compositions may comprise two or more hardeners, in order to obtain the required properties for the epoxy composite.
  • Blends of hardeners are commonly used when the epoxy composite requires excellent mechanical properties (such as high flexural strength, high tensile strength, high glass transition temperature (Tg), etc.) and when the epoxy composition requires sufficient time to flow and impregnate the reinforcement before fully curing.
  • the blades of wind turbines made from epoxy composites need to have good thermo-mechanical properties (e.g., good flexural and tensile strengths and a high Tg) to be suitable for use.
  • the epoxy compositions used to form the epoxy composite generally need to allow a mould for the blade (which is large in the case of a blade for a wind turbine) to be completely filled with the epoxy composition before fully curing or before the viscosity becomes too high due to curing.
  • a blend of hardeners is often used in the production of the blades for wind turbines.
  • a widely used blend comprises JEFFAMINE® D-230 (a polyether amine, commercially available from Huntsman Corporation) and a cycloaliphatic amine, such as isophorone diamine (IPDA).
  • IPDA isophorone diamine
  • a blend of hardeners is required because the polyether amine alone does not provide the required mechanical strength for the blade, and therefore the cycloaliphatic amine is added to enhance the mechanical strength.
  • use of the cycloaliphatic amine alone would not provide slower curing like the polyether amine, hindering production of the blade (or other epoxy composites).
  • an epoxy composite comprising: i) an epoxy composition as defined herein which is cured to form a cured epoxy composition, and ii) a reinforcement in contact with the cured epoxy composition.
  • the amine hardener component comprising an amine hardener of the structural formula (1) is particularly suited for epoxy compositions which are used to make epoxy composites, due to the excellent mechanical strength of the cured epoxy composition as well as the cure profile which allows the epoxy composition to flow and impregnate the reinforcement before fully curing. Moreover, the processability (or handleability) of the epoxy composition into an epoxy composite is improved due to very little carbamation of the amine hardener component, as evidenced in Figure 1 discussed below. Therefore, it is advantageous in terms of processability/handleability to use the amine hardener component disclosed herein in place of the current state of the art blends comprising IPDA and poly ether amines.
  • a method of producing the epoxy composite comprising: providing the epoxy composition as defined herein and a reinforcement; contacting the reinforcement with the epoxy composition to coat or impregnate the reinforcement with the epoxy composition; and curing the epoxy composition, wherein the cured epoxy composition is in contact with the reinforcement.
  • an epoxy composite obtainable by the method of producing an epoxy composite as described herein.
  • amine hardener component in the production of an epoxy composite, wherein the amine hardener component comprises an amine hardener of the structural formula (1):
  • Ri is independently selected from H and a C1-C20 hydrocarbon group; each R2 is independently selected from H and a C1-C5 hydrocarbon group; x is 1 or 2; y is 1 or 2; z is 1 or 2; x+y+z is 3 or 4; and n is 0 or 1.
  • Figure 1 shows carbamation tests for different amine hardeners.
  • the present disclosure relates to an epoxy composition for producing an epoxy composite, the epoxy composition comprising: i) an epoxy resin; and ii) an amine hardener component comprising an amine hardener of structural formula (1):
  • Ri is independently selected from H and a C1-C20 hydrocarbon group; each R2 is independently selected from H and a C1-C5 hydrocarbon group; x is 1 or 2; y is 1 or 2; z is 1 or 2; x+y+z is 3 or 4; and n is 0 or 1.
  • the present disclosure also relates to an epoxy composite comprising: i) a cured epoxy composition, wherein the epoxy composition comprises an epoxy resin and an amine hardener component comprising an amine hardener of structural formula (1): wherein Ri is independently selected from H and a C1-C20 hydrocarbon group; each R2 is independently selected from H and a C1-C5 hydrocarbon group; x is 1 or 2; y is 1 or 2; z is 1 or 2; x+y+z is 3 or 4; and n is 0 or 1, and ii) a reinforcement in contact with the cured epoxy composition.
  • Ri is independently selected from H and a C1-C20 hydrocarbon group
  • each R2 is independently selected from H and a C1-C5 hydrocarbon group
  • x is 1 or 2
  • y is 1 or 2
  • z is 1 or 2
  • x+y+z is 3 or 4
  • n is 0 or 1
  • ii) a reinforcement in contact with the cured epoxy composition wherein
  • the use of the above-defined amine hardener component comprising an amine hardener of the structural formula (1) in an epoxy composition allows for the required mechanical strength in an epoxy composite produced from the epoxy composition, while also allowing for a slow enough cure of the epoxy composition to allow a mould for the epoxy composite to be completely filled and the reinforcements to be impregnated.
  • the use of the above amine hardener component in an epoxy composition allows for improved handling of the epoxy composition because carbamation is significantly reduced compared with the current state of the art blends comprising IPDA. This is evidenced in Figure 1.
  • the epoxy composition of the present disclosure has improved handling relative to the current state of the art epoxy compositions comprising IPDA as a hardener.
  • the epoxy composition described herein has a slow enough curing time so that the composition can completely fill a mould for an epoxy composite without prematurely curing, thereby allowing the reinforcements to be impregnated with the epoxy composition, (ii) results in an epoxy composite having excellent mechanical properties, (iii) employs an amine hardener component which does not suffer from carbamation and therefore the hardener and composition have improved handling and processability, and (iv) is a simplified epoxy composition which may use fewer components (one type of hardener vs a blend of hardeners as used in the current state of the art hardeners for epoxy composites).
  • the epoxy resin is not particularly limited, and any known epoxy resin which is suitable for use in an epoxy composite may be used.
  • One or more epoxy resins may be used.
  • Suitable epoxy resins may include, but are not limited to, a polyglycidyl epoxy compound, a non-glycidyl epoxy compound, an epoxy cresol novolac compound, and an epoxy phenol novolac compound.
  • the polyglycidyl epoxy compound may be a polyglycidyl ether, poly (P- methylglycidyl) ether, polyglycidyl ester or poly(P-methylglycidyl) ester.
  • the ethers may be obtained by reacting a compound having at least one free alcoholic hydroxyl group and/or phenolic hydroxyl group with a suitably substituted epichlorohydrin under alkaline conditions or in the presence of an acidic catalyst followed by alkali treatment.
  • the alcohols may be, for example, acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycols, propane- 1,2-diol, poly(oxypropylene) glycols, propane- 1,3 -diol, butane- 1,4-diol, poly(oxytetramethylene) glycols, pentane- 1,5-diol, hexane-l,6-diol, hexane-2,4,6- triol, glycerol, 1,1,1 -trimethylolpropane, bistrimethylolpropane, pentaerythritol, and sorbitol.
  • acyclic alcohols such as ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycols, propane- 1,2-diol, poly(oxypropylene) glycols, propane- 1,3 -diol, butane- 1,4-diol, poly(
  • Suitable glycidyl ethers may also be obtained from cycloaliphatic alcohols, such as 1,3- or 1,4-dihydroxy cyclohexane, bis(4-hydroxycyclo- hexyl)methane, 2,2- bis(4-hydroxycyclohexyl)propane or 1,1- bis(hydroxymethyl)cyclohex-3-ene, or they may possess aromatic rings, such as N,N- bis(2-hydroxyethyl)aniline or p,p'- bis(2-hydroxyethylamino)diphenylmethane.
  • cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxy cyclohexane, bis(4-hydroxycyclo- hexyl)methane, 2,2- bis(4-hydroxycyclohexyl)propane or 1,1- bis(hydroxymethyl)cyclohex-3-ene, or they may possess aromatic rings, such as N,N- bis(2-hydroxyethyl)ani
  • Particularly important representatives of polyglycidyl ethers or poly([3- methylglycidyl)ethers may be based on monocyclic phenols, for example, on resorcinol or hydroquinone; on polycyclic phenols, for example, on bis(4- hydroxyphenyl)methane (bisphenol F), 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4- hydroxyphenyl)sulfone (bisphenol S), alkoxylated bisphenol A, F or S, triol extended bisphenol A, F or S, brominated bisphenol A, F or S, hydrogenated bisphenol A, F or S, glycidyl ethers of phenols and phenols with pendant groups or chains; on condensation products, obtained under acidic conditions, of phenols or cresols with formaldehyde, such as phenol novolaks and cresol novolaks; or on siloxane digly cidyls.
  • Polyglycidyl esters and poly(P-methylglycidyl)esters may be produced by reacting epichlorohydrin or glycerol dichlorohydrin or P-methylepichlorohydrin with a polycarboxylic acid compound. The reaction is expediently earned out in the presence of bases.
  • the polycarboxylic acid compounds may be, for example, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid.
  • cycloaliphatic polycarboxylic acids for example, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4- methylhexahydrophthalic acid.
  • the epoxy resin may comprise one or more bisphenol diglycidyl ether epoxy resins obtainable by reacting at least one bisphenol compound with epichlorohydrin.
  • the bisphenol compound may be any known bisphenol compound, such as bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C2, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, any derivative thereof, or any combination thereof.
  • the at least one bisphenol compound is bisphenol A and/or F.
  • the epoxy resin may comprise bisphenol A diglycidyl ether or a derivative thereof, bisphenol F digylcidyl ether or a derivative thereof, or a blend of bisphenol A diglycidyl ether or a derivative thereof and bisphenol F diglycidyl ether or a derivative thereof.
  • a blend of bisphenol resins is commonly used in the production of epoxy composites such as wind blades.
  • the epoxy resin may comprise a non-glycidyl epoxy compound. Non- glycidyl epoxy compounds may be linear, branched, or cyclic in structure.
  • epoxide compounds in which the epoxide groups form part of an alicyclic or heterocyclic ring system.
  • Others include an epoxy-containing compound with at least one epoxycyclohexyl group that is bonded directly or indirectly to a group containing at least one silicon atom.
  • Still others include epoxides which contain one or more cyclohexene oxide groups and epoxides which contain one or more cyclopentene oxide groups.
  • Non-glycidyl epoxy compounds may be formed by peroxidation of olefinic double bonds.
  • the epoxy resin may be a bio-based epoxy resin obtained by reacting epichlorohydrin with renewable precursors such as unsaturated vegetable oils, saccharides, tannins, cardanol, terpenes, rosins, furan, and lignin.
  • Unsaturated vegetable oils may comprise soybean oils, linseed, canola, sunflower and Karanja.
  • the epoxy resin may be a bio-based epoxy resin obtained by reacting bio-based epichlorohydrin with these renewable precursors.
  • the epoxy resin may be a biobased epoxy resin obtained by reacting bio-based epichlorohydrin with fuel-based precursors.
  • the weight ratio of the different compounds is not particularly limited, and the skilled person would adjust the weight ratio as required.
  • the purpose of the amine hardener component is to react with the epoxy resin in order to cure and harden the epoxy composition.
  • the amine hardener component comprises an amine hardener of structural formula (1): wherein Ri is independently selected from H and a C1-C20 hydrocarbon group; each R2 is independently selected from H and a C1-C5 hydrocarbon group; x is 1 or 2; y is 1 or 2; z is 1 or 2; x+y+z is 3 or 4; and n is 0 or 1.
  • hydrocarbon group refers to a linear or a branched aliphatic group containing H and C atoms, or an aromatic or non-aromatic cyclic group containing H and C atoms.
  • the hydrocarbon group may further contain heteroatoms, such as O, N and S, in the carbon chain, and may contain a halogen atom(s) in place of a hydrogen(s) in the carbon chain.
  • the hydrocarbon group may refer to an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or any combination thereof.
  • Ri may be independently selected from H and a Cl -CIO hydrocarbon group. In one embodiment, Ri may be independently selected from H and a C1-C5 hydrocarbon group.
  • the C1-C5 hydrocarbon group of Ri may be independently selected from a methyl, ethyl, propyl, butyl, and pentyl.
  • an “alkyl” group refers to all possible isomers of the alkyl group, e.g. propyl refers to either n- propyl or i-propyl, and butyl refers to any one of n-butyl, s-butyl, i-butyl, and t-butyl.
  • the C1-C5 hydrocarbon group of R2 may be independently selected from a methyl, ethyl, propyl, butyl, and pentyl.
  • Ri is independently any one selected from H, methyl (-CH3), and ethyl (-CH2CH3);
  • R2 is independently any one selected from H, -CH3 and -CH2CH3;
  • x is 1 or 2;
  • y is 1 or 2;
  • z is 1 or 2;
  • x+y+z is 3 or 4; and
  • n is 0 or 1.
  • x+y+z is 3. In one embodiment, x+y+z is 4. In one embodiment, x is 1; y is 1; and z is 1. In one embodiment, x is 2; y is 1; and z is 1. In one embodiment, x is 1; y is 2; and z is 1. In one embodiment, x is 1; y is 1; and z is 2.
  • n may be 0, 1, 2, 3, 4, or 5 in structural formula (1). In one embodiment, n is 0. In one embodiment, n is 1.
  • Ri is H. In one embodiment, Ri is -CH3. In one embodiment, Ri is -CH2CH3.
  • R2 is -CH3. In one embodiment, R2 is -CH2CH3.
  • n is 0 and Ri is H. In one embodiment, n is 0; Ri is H; x is 1; y is 1; z is 1 or 2. In one embodiment, n is 0; Ri is H; x is 1; y is 1; z is 1. In one embodiment, n is 0; Ri is H; x is 1; y is 1; z is 2. [0052] In one embodiment, n is 1 and Ri is -CH2CH3. In one embodiment, n is 1; Ri is - CH2CH3; x is 1; y is 1; z is 1. In one embodiment, n is 1; Ri is -CH2CH3; x is 1; y is 1; z is 2. In one embodiment, n is 1; Ri is -CH2CH3; x is 1; y is 2; z is 1.
  • the amine hardener preferably has the following structural formula (la): r 4.
  • x is 1; y is 1; and z is 1. In one embodiment, in structural formula (la), x is 1; y is 1; and z is 2.
  • amine hardener component refers to a composition comprising at least an amine hardener of structural formula (1).
  • the amine hardener component may comprise additional compounds (such as additional amine hardeners) besides amine hardeners of structural formula (1).
  • the amine hardener component is obtainable by reacting an initiator of structural formula (2) with one or more alkylene oxides, followed by reductive amination using hydrogen and ammonia, to form the amine hardener component comprising an amine hardener of structural formula (1), wherein 1 mole equivalent of initiator is reacted with about 3 to about 5, or about 3 to about 4, or preferably about 3.5, mole equivalents of the one or more alkylene oxides, and structural formula (2) is as follows: wherein n and Ri are as defined in structural formula (1).
  • reaction product of reacting the initiator of structural formula (2) with one or more alkylene oxides, followed by reductive amination using hydrogen and ammonia may be used as the amine hardener component without isolation of the amine hardener of structural formula (1).
  • the amine hardener component may comprise an amine hardener of structural formula (F).
  • the amine hardener component When the amine hardener component is obtained by reacting an initiator of structural formula (2) with one or more alkylene oxides, followed by reductive amination using hydrogen and ammonia, the amine hardener may have a structural formula (T).
  • Structural formula (F) is a modified version of structural formula (1), modified in that in structural formula (1’): x+y+z is 0-30, x is 0-20, y is 0-20 and z is 0-20.
  • no other hardeners may be present in the amine hardener component except from amine hardeners having the structure of structural formula (1) and modified structural formula (1 ’).
  • the epoxy composition comprises only one type of amine hardener, unlike the current state of the art blends of amine hardeners which typically comprise IPDA and a polyether amine.
  • amine hardeners which typically comprise IPDA and a polyether amine.
  • the replacement of a blend of hardeners with a single type of hardener simplifies the epoxy system.
  • the amine hardener component may consist of an amine hardener of structural formula (1). This may be the case when the amine hardener component is obtained by reacting an initiator of structural formula (2) with one or more alkylene oxides, followed by reductive amination using hydrogen and ammonia, and further followed by purifying and isolating the amine hardener of structural formula (1).
  • the isolated amine hardener of structural formula (1) may be used as the amine hardener component.
  • the amine hardener component comprising an amine hardener of structural formula (1) may be prepared by reacting an alkylene oxide (such as ethylene oxide, propylene oxide, and/or butylene oxide) with a suitable initiator of structural formula (2) to prepare an intermediate polyol.
  • Suitable initiators include glycerol, trimethylolpropane, or any derivative thereof.
  • Structural formula (2) is: [0062] wherein n and Ri are as defined in structural formula (1).
  • the intermediate polyol is typically prepared by charging the initiator or derivative in the alkoxylation reaction zone and then contacting it with at least one alkylene oxide (such as ethylene oxide, propylene oxide, and/or butylene oxide) for a period of time sufficient to provide the polyol.
  • alkylene oxide such as ethylene oxide, propylene oxide, and/or butylene oxide
  • the amount of alkylene oxide which is contacted with the initiator may range from about 2 to about 5 moles of alkylene oxide per mole of initiator, or about 3 to about 5 moles, or about 3 to about 4 moles, and preferably about 3.5 moles, of alkylene oxide per mole of initiator. Additionally, the period of time the initiator is contacted with alkylene oxide is a period of time sufficient to form the intermediate polyol, and in some instances may range from about 0.5 hours to about 24 hours.
  • the alkoxylation reaction zone can be a closed reaction vessel with alkoxylation being carried out under elevated temperature and pressure and in the presence of a base catalyst or a double metal cyanide (DMC) catalyst.
  • alkoxylation may be conducted at a temperature ranging from about 50°C to about 150°C and at a pressure ranging from about 40 psi to about 100 psi.
  • the base catalyst may be any alkaline compound customarily used for base-catalyzed reactions, for example, an alkali metal hydroxide such as sodium hydroxide, lithium hydroxide, potassium hydroxide, or caesium hydroxide, or a tertiary amine such as dimethyl cyclohexylamine or 1,1,3,3-tetramethylguanidine.
  • an alkali metal hydroxide such as sodium hydroxide, lithium hydroxide, potassium hydroxide, or caesium hydroxide
  • a tertiary amine such as dimethyl cyclohexylamine or 1,1,3,3-tetramethylguanidine.
  • the intermediate polyol is then used as a feedstock in a reductive amination step to form the amine hardener of structural formula (1).
  • about 2 to 5 mole equivalents, or about 3 to 5 equivalents, or about 3 to 4 equivalents, or 3.5 equivalents, of alkylene oxide is reacted with 1 mole equivalent of initiator.
  • the intermediate polyol is neutralized with acid or a chemical adsorbent, such as for example, oxalic acid or magnesium silicate, and filtered for the removal of insoluble materials.
  • a chemical adsorbent such as for example, oxalic acid or magnesium silicate
  • the intermediate polyol is charged to a reductive amination zone where it is brought into contact with a reductive amination catalyst, sometimes referred to as a hydrogenation-dehydrogenation catalyst, and reductively aminated in the presence of hydrogen and ammonia under reductive amination conditions.
  • Reductive amination conditions may include, for example, a temperature within the range of about 150°C to about 275°C and a pressure within the range of about 500 psi to about 5000 psi or with a temperature within the range of about 180°C to about 220°C and pressure within the range of about 100 psi to about 2500 psi.
  • the hydrogenation catalyst may comprise one or more of the metals of group VI I IB of the Periodic Table, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, and platinum, mixed with one or more metals of group VIB of the Periodic Table such as chromium, molybdenum, or tungsten.
  • a promoter from group IB of the Periodic Table, such as copper, may also be included.
  • a catalyst may be used comprising from about 60 mole percent to about 85 mole percent of nickel, about 14 mole percent to about 37 mole percent of copper and about 1 mole percent to about 5 mole percent of chromium (as chromia), such as a catalyst of the type disclosed in U.S. Pat. No. 3,152,998.
  • a catalyst of the type disclosed in U.S. Pat. No. 4,014,933 may be used containing from about 70% by weight to about 95% by weight of a mixture of cobalt and nickel and from about 5% by weight to about 30% by weight of iron.
  • 4,152,353 may be used, comprising nickel, copper and a third component which may be iron, zinc, zirconium, or a mixture thereof, for example, a catalyst containing from about 20% by weight to about 49% by weight of nickel, about 36% by weight to about 79% by weight of copper, and about 1 % by weight to about 15% by weight of iron, zinc, zirconium, or a mixture thereof.
  • a catalyst of the type described in U.S. Pat. No. 4,766,245 may be used comprising about 60% by weight to about 75% by weight of nickel, and about 25% by weight to about 40% by weight of aluminium.
  • the reductive amination may be conducted on a continuous basis with the intermediate polyol, ammonia, and hydrogen being continuously charged to a reactor containing a fixed bed of reductive amination catalyst and with reaction mixture being continually withdrawn.
  • reaction mixture resulting from reductive amination may be suitably depressured so as to recover excess hydrogen and ammonia for recycling and is then fractionated to remove by-product water to provide the reaction product comprising the amine hardener of structural formula (1).
  • the reaction product comprising the amine hardener of structural formula (1) may be used as the amine hardener component in the epoxy composition.
  • the reductive amination conditions which may also be utilized include the use of from about 4 moles to about 150 moles of ammonia per hydroxyl equivalent of intermediate polyol feedstock.
  • Hydrogen may be used in an amount ranging from about 0.5 mole equivalents to about 10 mole equivalents of hydrogen per hydroxyl equivalent of intermediate polyol feedstock.
  • the contact times within the reaction zone, when the reaction is conducted on a batch basis may be within the range of from about 0.1 hours to about 6 hours, or from about 0.15 hours to about 2 hours.
  • reaction times may be from about 0.1 grams to about 2 grams of feedstock per hour per cubic centimeter of catalyst and, more preferably, from about 0.3 grams to about 1 .6 grams of precursor feedstock per hour per cubic centimeter of catalyst.
  • the reductive amination may be conducted in the presence of about 1 mole to about 200 moles of ammonia per mole of intermediate polyol, or from about 4 moles to about 130 moles of ammonia per mole of intermediate polyol. From about 0.1 moles to about 50 moles of hydrogen per mole of intermediate polyol may be employed, or from about 1 mole to about 25 moles of hydrogen per mole of intermediate polyol.
  • the reaction product comprising the amine hardener of structural formula (1) may contain amine compounds in addition to the amine hardeners of structural formula (1). That is, other amine compounds may be present in the reaction product obtainable by the above-described process, including amine compounds of structural formula (F) described above.
  • the reaction product would however contain amine hardeners wherein x is 1 or 2, y is 1 or 2, z is 1 or 2, and x+y+z is 3 or 4.
  • the average value of x+y+z in structural formula (1) is preferably from 3 to 4.
  • the amine hardener of structural formula (1) is isolated from the reaction product comprising the amine hardener of structural formula (1). Any known method to isolate the amine hardener may be used.
  • the amine hardener of structural formula (1) may be obtained by reacting an initiator of structural formula (2) with butylene oxide and/or propylene oxide, followed by reductive amination using hydrogen and ammonia, to form a reaction product, wherein about 1 mole equivalent of initiator is reacted with about 3-4 mole equivalents (preferably about 3.5 mole equivalents) of butylene oxide and/or propylene oxide.
  • the amine hardener of structural formula (1) may be obtained by reacting an initiator of structural formula (2) with propylene oxide, followed by reductive amination using hydrogen and ammonia, wherein 1 mole equivalent of initiator is reacted with about 3.5 mole equivalents of propylene oxide.
  • the amine hardener of structural formula (1) may be obtained by reacting an initiator of structural formula (2) with butylene oxide, followed by reductive amination using hydrogen and ammonia, wherein 1 mole equivalent of initiator is reacted with 3.5 mole equivalents of butylene oxide.
  • the initiator is preferably glycerol or trimethylolpropane, preferably glycerol, and the alkylene oxide is preferably propylene oxide.
  • the amine hardener of structural formula (1) may be isolated from the reaction product.
  • the reaction product comprising the amine hardener of structural formula (1) may be used as the amine hardener component without isolating the amine hardener of structural formula (1).
  • the reaction product described above may be used as the amine hardener component comprising an amine hardener of a structural formula (1).
  • the epoxy composition may comprise at least one epoxy diluent, such as a compound selected from alkyl (Cl 2- Cl 4) glycidyl ether, p-tertiary butyl phenol glycidyl ether, cresyl glycidyl ether, 1,4-butanediol di glycidyl ether, cyclohexane dimethylol diglycidyl ether, resorcinol diglycidyl ether, trimethylol propane triglycidyl ether, glycerol trigly cidyl ether, neopentyl glycol diglycidyl ether, or any combination thereof.
  • the epoxy composition may comprise about 0-20 wt% of the epoxy diluent, or about 2-15 wt%, or about 5-10 wt%, based upon the total weight of the epoxy composition.
  • the epoxy composition may further comprise at least one additive selected from a thermoplastic particle, a flexibilizer, a toughening agent, an accelerator, a core shell rubber, a wetting agent, a flame retardant, a pigment or dye, a plasticizer, water, a solvent, a UV absorber, a viscosity modifier, a filler, a conducting particle, or any combination thereof.
  • at least one additive selected from a thermoplastic particle, a flexibilizer, a toughening agent, an accelerator, a core shell rubber, a wetting agent, a flame retardant, a pigment or dye, a plasticizer, water, a solvent, a UV absorber, a viscosity modifier, a filler, a conducting particle, or any combination thereof.
  • the “amine/epoxy stoichiometric ratio” refers to the ratio of the number of amine hydrogen bonds (i.e., -N-H bonds) of the amine hardener to the number of epoxy groups of the epoxy resin.
  • an amine/epoxy stoichiometric ratio of 1 : 1 means that the amine hardener and epoxy resin have an equal number of amine hydrogen bonds and epoxy groups.
  • the amine/epoxy stoichiometric ratio is from 0.5: 1 to 3 : 1, or from 1 : 1 to 3 : 1, or from 2: 1 to 3 : 1, or 3 : 1.
  • the amine hardener according to the present disclosure may have six -N-H bonds, and in one embodiment the epoxy resin has two epoxy groups.
  • the epoxy composition comprises about 10-100 parts by weight of amine hardener to 100 parts by weight of epoxy resin, or about 10-90 parts by weight of amine hardener to 100 parts by weight of epoxy resin, or about 10-80 parts by weight of amine hardener to 100 parts by weight of epoxy resin, or about 10-70 parts by weight of amine hardener to 100 parts by weight of epoxy resin, or about 10-60 parts by weight of amine hardener to 100 parts by weight of epoxy resin, or about 10-50 parts by weight of amine hardener to 100 parts by weight of epoxy resin, or about 15-45 parts by weight of amine hardener to 100 parts by weight of epoxy resin, or about 20-40 parts by weight of amine hardener to 100 parts by weight of epoxy resin, or about 25-35 parts by weight of amine hardener to 100 parts by weight of epoxy resin.
  • the epoxy composition reaches a viscosity of 1 Pa.s in a time of 40 minutes or more, or 45 minutes or more, or 50 minutes or more, or 55 minutes or more, or from 40 minutes to 150 minutes, or from 45 minutes to 145 minutes, or from 45 minutes to 140 minutes, or from 45 minutes to 135 minutes, at a temperature of 40°C.
  • the epoxy composition reaches a viscosity of 2 Pa.s in a time of 75 minutes or more, or 80 minutes or more, or 85 minutes or more, or 90 minutes or more, or from 75 minutes to 130 minutes, or from 75 minutes to 125 minutes, or from 80 minutes to 120 minutes, at a temperature of 40°C.
  • the epoxy composition reaches a viscosity of 5 Pa.s in a time of 120 minutes or more, or 125 minutes or more, or 130 minutes or more, or 135 minutes or more, or from 120 minutes to 250 minutes, or from 120 minutes to 225 minutes, or from 120 minutes to 200 minutes, at a temperature of 40°C. In one embodiment, the epoxy composition reaches a viscosity of 10 Pa.s in a time of 125 minutes, or 150 minutes or more, or 155 minutes or more, or 160 minutes or more, or 165 minutes or more, or from 150 minutes to 300 minutes, or from 150 minutes to 250 minutes, or from 150 minutes to 225 minutes, at a temperature of 40°C.
  • the viscosity profile described above gives sufficient time for the epoxy composition to effectively impregnate the reinforcements of a large composite.
  • the time to reach viscosity is indicative of the reactivity of the epoxy composition, and the less time it takes to reach a specific viscosity indicates a higher reactivity.
  • the time to reach viscosity is measured at 40°C using an Anton Paar Rheometer (model no. MRC302e).
  • the cured epoxy composition may have the following mechanical properties (without the reinforcement in the epoxy composite being present).
  • the “cured epoxy composition” used herein refers to the hardening of the epoxy resin by chemical crosslinking, such that the amine hardener component and the epoxy resin have reacted such that one or both components are substantially consumed. Typically, this is achieved by heating the epoxy composition for a prolonged period of time, known as a cure cycle. More specifically, a “cure cycle” as used herein means the period over which a curable epoxy composition is heated, wherein the heat applied is (i) increased from ambient temperature to a set cure temperature, (ii) held at the set cure temperature for a period of time, and (iii) cooled back to ambient temperature.
  • An example of a suitable cure cycle is heating from ambient temperature to from about 60°C to about 100°C for about 60 minutes to 180 minutes followed by heating to from about 100° to about 150°C for about 120 minutes to about 240 minutes, followed by cooling to ambient temperature.
  • Another example of a suitable cure cycle is to heat the curable epoxy composition from ambient temperature to from about 60° to about 100°C for about 4 hours to about 8 hours.
  • “Ambient temperature” refers to room temperature, or the temperature of the environment under normal conditions.
  • the cured epoxy composition has a glass transition temperature (Tg) of at least about 50°C, or at least about 55°C, or at least about 60°C, or at least about 65°C, or at least about 70°C, or at least about 75°C, or from about 50°C to about 200°C, or from about 60°C to about 150°C, or from about 70°C to about 125°C.
  • Tg glass transition temperature
  • the epoxy composition is particularly suited for use in epoxy composites.
  • the Tg is measured by subjecting the cured epoxy composition to differential scanning calorimetry (DSC, using a DSC-250 from TA instruments), using the following parameters:
  • the Tg is measured on the 3 rd run (2 nd heating run), and corresponds to the inflection point (defined as the steepest point of the glass transition step) in the DSC graph.
  • the cured epoxy composition has an elongation at break of from about 0.1% to about 15%, or from about 0.5% to about 12.5%, or from about 1% to about 10%.
  • the elongation at break is measured according to ASTM D638-22, at a tensile rate of 5 mm/min.
  • the cured epoxy composition has a tensile strength of at least about 50 MPa, or at least about 55 MPa, or at least about 60 MPa, or at least about 65 MPa, or at least about 70 MPa, or from about 50 MPa to about 500 MPa, or from about 60 MPa to about 400 MPa, or from about 70 MPa to about 300 MPa.
  • the tensile strength is measured according to ASTM D638-22, at a tensile rate of 5 mm/min.
  • the cured epoxy composition has a tensile modulus of at least about 1 GPa, or at least about 1.5 GPa, or at least about 2 GPa, or at least about 2.1 GPa, or at least about 2.2 GPa, or at least about 2.3 GPa, or at least about 2.4 GPa, or at least about 2.5 GPa, or at least about 2.6 GPa, or at least about 2.7 GPa, or at least about 2.8 GPa, or at least about 2.9 GPa, or at least about 3 GPa, or from about 1 GPa to about 50 GPa, or from about 1.5 GPa to about 25 GPa, or from about 2 GPa to about 20 GPa.
  • the tensile modulus is measured according to ASTM D638- 22, at a tensile rate of 5 mm/min .
  • the cured epoxy composition has a flexural strength of at least about 70 MPa, or at least about 80 MPa, or at least about 90 MPa, or at least about 95 MPa, or at least about 100 MPa, or from about 70 MPa to about 500 MPa, or from about 80 MPa to about 250 MPa, or from about 90 MPa to about 200 MPa.
  • the flexural strength is measured according to ASTM D790-17, at a flex speed of 10 mm/min.
  • the cured epoxy composition has a flexural modulus of at least about 1 GPa, or at least about 1.5 GPa, or at least about 2 GPa, or at least about 2.1 GPa, or at least about 2.2 GPa, or at least about 2.3 GPa, or at least about 2.4 GPa, or at least about 2.5 GPa, or at least about 2.6 GPa, or at least about 2.7 GPa, or at least about 2.8 GPa, or at least about 2.9 GPa, or at least about 3 GPa, or from about 1 GPa to about 50 GPa, or from about 1.5 GPa to about 25 GPa, or from about 2 GPa to about 20 GPa.
  • the flexural modulus is measured according to ASTM D790- 17.
  • the cured epoxy composition has a Shore D hardness after 10 seconds of at least about 60, or at least about 65, or at least about 70, or from about 60 to about 100, or from about 70 to about 99.
  • the Shore D hardness is measured according to ASTM D2240-15.
  • the epoxy composite made therefrom has excellent mechanical properties which are particularly suited for epoxy composites.
  • the epoxy composite according to the present disclosure comprises the epoxy composition as described herein which is cured to form a cured epoxy composition, and a reinforcement in contact with the cured epoxy composition.
  • the epoxy composition may be fully cured to form the epoxy composite.
  • the reinforcement is in contact with the cured epoxy composition.
  • the reinforcement is distributed within the matrix formed by the cured epoxy composition.
  • the reinforcement may provide strength to the composite.
  • the reinforcement is any one selected from a fiber, a particulate, a filler, a flake, and a combination thereof.
  • the reinforcement is a fiber.
  • the fibers can be in continuous, chopped and/or fabric form.
  • a carbon fiber for e.g., polyacrylonitrile (PAN)-based carbon fiber, a pitch-based carbon fiber, and a vapor-grown carbon fiber
  • a glass fiber for e.g., polyacrylonitrile (PAN)-based carbon fiber, a pitch-based carbon fiber, and a vapor-grown carbon fiber
  • PAN polyacrylonitrile
  • a glass fiber for e.g., polyacrylonitrile (PAN)-based carbon fiber, a pitch-based carbon fiber, and a vapor-grown carbon fiber
  • PAN polyacrylonitrile
  • aramid fiber for e.g., polyacrylonitrile (PAN)-based carbon fiber, a pitch-based carbon fiber, and a vapor-grown carbon fiber
  • a glass fiber for e.g., polyacrylonitrile (PAN)-based carbon fiber, a pitch-based carbon fiber, and a vapor-grown carbon fiber
  • aramid fiber for e.g., polyacrylonitrile
  • concentrations of the reinforcement in the epoxy composition of the present disclosure may vary from about 0.2 parts by weight to about 95 parts by weight, or between about 0.2 parts by weight to about 70 parts by weight, or between about 0.2 parts by weight to about 60 parts by weight, based on 100 parts by weight of the epoxy composition.
  • the epoxy composite may be a wind turbine component, a pressure vessel component, a pipe, a fitting, a tank, a boat component or a composite tool.
  • the epoxy composite is a wind turbine component, it is preferable that the component is a blade.
  • the epoxy composition and epoxy composite as described herein are particularly suited for large epoxy composite applications such as wind turbine components such as blades.
  • the present disclosure provides a method of producing the epoxy composite, comprising: providing the epoxy composition as defined herein and a reinforcement; contacting the reinforcement with the epoxy composition to coat or impregnate the reinforcement with the epoxy composition; and curing the epoxy composition, wherein the cured epoxy composition is in contact with the reinforcement.
  • the method of curing the epoxy composition may comprise heating the epoxy composition according to a cure cycle.
  • the epoxy composition may be heated at a set cure temperature ranging from about 60°C to about 220°C, or from about 60°C to about 200°C, or from about 60 to about 180°C for a time sufficient to cure the epoxy composition and produce an epoxy composite.
  • the time sufficient may be in a range of from about 2 minutes to about 24 hours, or from about 15 minutes to about 10 hours, or from about 30 minutes to about 6 hours.
  • the set cure temperature may be attained by heating the epoxy composition at a rate in a range of from about 0.1 °C per minute to about 25°C per minute, or from about 0.5°C per minute to about 10°C per minute, or from about 1°C per minute to about 10°C per minute, or from about 2°C per minute to about 10°C per minute, or from about 3°C per minute to about 10°C per minute, or from about 4°C per minute to about 10°C per minute, or from about 5°C per minute to about 10°C per minute, or from about 5°C per minute to about 10°C, or from about 6°C per minute to about 10°C per minute, or from about 7°C per minute to about 10°C per minute, until the set cure temperature is achieved.
  • the set cure temperature is immediately reached (e.g., via a preheated oven) and the epoxy composition is heated at the set cure temperature for a time sufficient to cure the epoxy composition and produce an epoxy composite.
  • This technique is used in, for example, liquid resin processing methods (e.g., injection molding).
  • the epoxy composite may be produced using a mould, e.g., via a resin transfer moulding (RTM) system.
  • the method comprises: a) introducing a fiber preform comprising fibers into a mould; b) injecting the epoxy composition into the mould, c) allowing the epoxy composition to impregnate the fiber preform; and d) heating the epoxy composition impregnated preform for a period of time sufficient to produce an epoxy composite.
  • there is an additional step namely step e) subjecting the epoxy composite to post curing operations at an elevated temperature such as from about 100°C to about 250°C.
  • a release agent may be added to the mould to help remove the epoxy composite from the mould. Any known release agents in the art may be used, as long as they are compatible with the epoxy composition used.
  • the epoxy composite is a wind turbine blade.
  • the wind turbine blades may be produced by a process in which a corresponding mould is provided, the epoxy composition is introduced into this mould, and the epoxy composition is cured to completion only when the mould has been completely filled.
  • the epoxy composition is introduced into the corresponding mould in some embodiments by way of infusion technology.
  • a vacuum may be applied to the moulding. This vacuum draws the epoxy composition into the mould under suction at temperatures below the initial curing temperature, and so the viscosity during the filling operation remains virtually unchanged and all of the regions of the moulding are filled before fully curing.
  • This is followed by complete curing of the epoxy composition in the moulding at a suitable temperature, e.g., at least about 60°C, or between about 60° to about 120°C, for a suitable time length.
  • the present disclosure provides use of the amine hardener component as described herein in the production of an epoxy composite.
  • the components and properties of the epoxy composition and epoxy composite may be as described above, and the method of making the epoxy composite using the amine hardener component may be as described above.
  • an epoxy composition for producing an epoxy composite comprising: i) an epoxy resin; and ii) an amine hardener component comprising an amine hardener of structural formula (1):
  • an epoxy composite comprising: i) an epoxy composition as described herein which is cured to form a cured epoxy composition, and ii) a reinforcement in contact with the cured epoxy composition, wherein the reinforcement is a fiber.
  • a wind turbine component comprising: i) an epoxy composition as described herein which is cured to form a cured epoxy composition, and ii) a reinforcement in contact with the cured epoxy composition, wherein the reinforcement is a fiber.
  • Hl (amine hardener component) comprises amine hardeners of the following structure: wherein x is 1 or 2, y is 1 or 2, z is 1 or 2, and x+y+z is 3 or 4.
  • Hl was produced by reacting glycerol (1 mol equiv.) with propylene oxide (3.5 mol equiv.), followed by reductive amination using ammonia and hydrogen. 2000 g. of glycerol were mixed with 43.5 grams of 45% KOH solution in a 15L alkoxylation reactor. Water was removed from the mixture by heating under vacuum, then the autoclave was purged with nitrogen and 4414.8 grams of propylene oxide (PO) were added to the reactor over a period of 90 minutes. The mixture was allowed to digest for an additional 5 hours at 120° C and afterwards nitrogen was used to strip volatile compounds.
  • glycerol 1 mol equiv.
  • propylene oxide 3.5 mol equiv.
  • Hl comprises a mixture of amine compounds, some of which are according to structure formulae (1) and (E).
  • H2 hardener
  • IPDA available from Evonik
  • ER1 epoxy resin based on bisphenol A (commercially available from Huntsman corporation as Araldite®GY250)
  • ER2 epoxy resin
  • blend of a bisphenol A resin produced from bisphenol A and epichlorohydrin
  • a bisphenol F resin produced from bisphenol F and epichlorohydrin
  • EPIKOTETM Resin MGS RIMR035c Westlake Epoxy as EPIKOTETM Resin MGS RIMR035c
  • Example 1 and Reference Example 1 [0132] Example 1 and Reference Example 1:
  • Epoxy compositions of Example 1 and Reference Example 1 were prepared by mixing stoichiometric amounts of epoxy resin and amine hardener component, as indicated in the Table 1 below. Pbw indicates parts by weight. The epoxy compositions were then cured in a mould using a cure cycle of 2 hours at 80°C followed by 3 hours at 125°C. The mechanical properties of the cured epoxy compositions were then measured, as indicated in Table 1 below.
  • Example 1 is according to the present disclosure.
  • Reference Example 1 is not according to the present disclosure as the amine hardener component is a blend of IPDA and a poly etheramine.
  • the mechanical properties of the cured epoxy composition of Example 1 are comparable to the mechanical properties of the cured epoxy composition of Reference Example 1.
  • the mechanical properties of the cured epoxy composition according to the present disclosure are excellent, and the use of a single type of amine hardener (in place of the usual blend of amine hardeners) as discussed herein does not compromise the mechanical properties of the cured epoxy composition.
  • Table 2 below shows the time to reach viscosity for the epoxy compositions of Example 1 and Reference Example 1, at 40°C.
  • the epoxy composition of the present disclosure (Example 1) has comparable reactivity to the epoxy composition of Reference Example 1, and therefore the use of a single type of amine hardener (in place of the usual blend of amine hardeners) as discussed herein does not significantly affect the reactivity of the epoxy composition. If anything, there is more time to fill a mould using the epoxy composition as described herein.
  • Epoxy compositions of Examples 2 and 3 (Ex. 2 and Ex. 3) and Reference Examples 2 and 3 (Ref. Ex. 2 and Ref. Ex. 3) were prepared by mixing stoichiometric amounts of epoxy resin and amine hardener component, as indicated in the Table 3, below. Pbw indicates parts by weight. The epoxy compositions were then cured in a mould using a cure cycle of 6 hours at 80°C. The mechanical properties of the cured epoxy compositions were then measured, as indicated in Table 3, below.
  • Examples 2 and 3 are according to the present disclosure.
  • Reference Examples 2 and 3 are not according to the present disclosure as the amine hardener component is a blend of IPDA and a polyetheramine.
  • the mechanical properties of the cured epoxy compositions of Examples 2 and 3 are comparable to the mechanical properties of the cured epoxy compositions of Reference Examples 2 and 3.
  • the mechanical properties of the cured epoxy compositions according to the present disclosure are excellent, and the use of a single type of amine hardener (in place of the usual blend of amine hardeners) as discussed herein does not compromise the mechanical properties of the cured epoxy composition.
  • Carbamation tests - amine hardener Carbamation tests - amine hardener:
  • Amine hardeners tested pure IPDA; JEFFAMINE®D230/IPDA (70:30 by weight) corresponding to amine hardener H2; and amine hardener component Hl.
  • Carbamation test 8 grams of amine hardener was placed in glass tray on graph paper and left at room temperature and atmospheric pressure, and visually analysed at 0 days, 1 day, 7 days and 18 days by photograph (see Figure 1).
  • Figure la shows the photographs of IPDA;
  • Figure lb shows the photographs of H2; and
  • Figure 1c shows the photographs of Hl.
  • IPDA and H2 were significantly reduced in transparency and IPDA had turned to a powder.
  • Hl is highly stable to carbamation as evidenced by the transparency of Hl over 18 days, whereas H2 and IPDA are highly reactive to carbon dioxide as evidenced by the lack of transparency of H2 and IPDA over 18 days.
  • carbamation occurs, the transparency of the amine hardener reduces due to formation of a solid.

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Abstract

L'invention concerne une composition époxy destinée à la production d'un composite époxy, la composition époxy comprenant : une résine époxy ; et un composant durcisseur aminé comprenant un durcisseur aminé de formule structurale (1), R1 étant indépendamment choisi parmi H et un groupe hydrocarboné en C1-C20 ; chaque R2 étant indépendamment choisi parmi H et un groupe hydrocarboné en C1-C5 ; x valant 1 ou 2 ; y valant 1 ou 2 ; z valant 1 ou 2 ; x + y + z valant 3 ou 4 ; et n valant 0 ou 1.
PCT/EP2025/055294 2024-03-15 2025-02-27 Composition époxy pour la production d'un composite époxy Pending WO2025190675A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3152998A (en) 1960-06-08 1964-10-13 Jefferson Chem Co Inc Nickel-copper-chromia catalyst and the preparation thereof
US4014933A (en) 1969-10-23 1977-03-29 Basf Aktiengesellschaft Production of amines from alcohols
US4152353A (en) 1977-08-29 1979-05-01 The Dow Chemical Company Method of producing amines from alcohols, aldehydes, ketones and mixtures thereof
US4766245A (en) 1985-03-01 1988-08-23 Texaco Inc. Process for the preparation of polyoxyalkylene polyamines
EP3472221B1 (fr) * 2016-06-16 2021-11-10 Huntsman Petrochemical LLC Mélange pour durcir des compositions de résine epoxy
WO2023010442A1 (fr) * 2021-08-05 2023-02-09 Evonik Operations Gmbh Composition d'amine, système époxyde préparé à partir de la composition d'amine et d'une résine époxyde, et utilisation du système époxyde

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3152998A (en) 1960-06-08 1964-10-13 Jefferson Chem Co Inc Nickel-copper-chromia catalyst and the preparation thereof
US4014933A (en) 1969-10-23 1977-03-29 Basf Aktiengesellschaft Production of amines from alcohols
US4152353A (en) 1977-08-29 1979-05-01 The Dow Chemical Company Method of producing amines from alcohols, aldehydes, ketones and mixtures thereof
US4766245A (en) 1985-03-01 1988-08-23 Texaco Inc. Process for the preparation of polyoxyalkylene polyamines
EP3472221B1 (fr) * 2016-06-16 2021-11-10 Huntsman Petrochemical LLC Mélange pour durcir des compositions de résine epoxy
WO2023010442A1 (fr) * 2021-08-05 2023-02-09 Evonik Operations Gmbh Composition d'amine, système époxyde préparé à partir de la composition d'amine et d'une résine époxyde, et utilisation du système époxyde

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